Synthesis of aniline from dinitrogen and benzene mediated by supported sodium on magnesium oxide

The activation and transformation of small molecules such as dinitrogen (N2) and benzene has been a long-sought-after objective in synthetic chemistry. However, it remains a formidable challenge due to the chemical inertness of the highly robust N≡N and aryl C-H bonds. On the other hand, one of the significant challenges in C-N bond formation is the competitive adsorption and activation of N2 and benzene. Here we report the sodium supported on magnesium oxide (Na/MgO) nanoparticles possess reactive sites for the activation of both N2 and benzene, leading to C-N bond formation and providing the anilines with high selectivity on further protonation. The interplay of sodium, magnesium, and hydride species at the interface of Na and MgO plays a key role in N2 reduction and hydrogenation to NHx species, which then deprotonate the aryl C-H bond resulting in the formation of sodium anilide on MgO. The subsequent protonation of sodium anilide produces aniline with a high selectivity (>90%). This work demonstrates a strategy for the transformation of N2 and simple arenes into organic nitrogen-containing compounds via a solid surface-mediated process.